CN103923344A - Flame retardant, flame-retardant resin composition and molded body - Google Patents

Flame retardant, flame-retardant resin composition and molded body Download PDF

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CN103923344A
CN103923344A CN201410116859.9A CN201410116859A CN103923344A CN 103923344 A CN103923344 A CN 103923344A CN 201410116859 A CN201410116859 A CN 201410116859A CN 103923344 A CN103923344 A CN 103923344A
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compound
fire retardant
quality ppm
formed body
comparative example
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松井诚二
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Konoshima Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

A flame retardant includes magnesium-hydroxide particles that contain at least one transitional metal compound. The at least one transitional metal compound is at least one compound selected from a group consisting of copper compound, cobalt compound, nickel compound, zinc compound and titanium compound. The at least one transitional metal compound is contained in the magnesium-hydroxide particles with the content of 100 to 1000 mass ppm in terms of metals. In addition, the total content of the copper compound, the cobalt compound and the nickel compound is 1000 mass ppm in terms of metals or less while the total content of the zinc compound and the titanium compound is 1000 mass ppm or less.

Description

Fire retardant, flame retardant resin composition and formed body
The application is to be that October 24, application number in 2006 are that 200680001604.1 (international application no is PCT/JP2006/321132), denomination of invention are the divisional application of the application of " fire retardant, flame retardant resin composition and formed body " applying date.
Technical field
The present invention relates to magnesium hydroxide based flame retardant and the flame retardant resin composition that contains this fire retardant and formed body thereof as so-called Halogen based flame retardant.
Background technology
Thermoplastic resin due to forming process and electrical insulating property good and cheap, therefore be widely used in thin wire coating material and the wallpaper etc. of cable, household appliances, automobile etc. within doors.At present, a large amount of polyvinyl chloride resins that use in such use.
But the cable of use polyvinyl chloride resin etc. produces a large amount of cigarettes in the time of presence of fire, brings obstacle in the enclosed spaces such as underground street, subway, boats and ships to take refuge action or action, and secondary disaster may occur.Even also few resin material of the generation of therefore wishing to produce while developing fire the obnoxious flavoures such as the few burning of cigarette carbon monoxide.And recently, polyvinyl chloride resin people are also worried to the environmental problem of the initiations such as Dioxins (dioxin), therefore more keep someone at a respectful distance.
Therefore, Halogen resinoid is replaced by resins such as such as polyolefinss gradually.But polyolefin resin is more inflammable than polyvinyl chloride resin, in order to make fire-retardantization of polyolefin resin, is just studying and adding magnesium hydroxide compounds as Halogen based flame retardant.
For example, magnesium hydroxide based flame retardant has been proposed, wherein, to be converted into metal be 0.01 % by weight following (referring to patent documentation 1) to the total content of iron cpd, manganic compound, cobalt compound, chromium cpd, copper compound, palladium compound and nickel compound.By reducing the amount of above-mentioned transition metal, the resistance to thermal deterioration while improveing melting mixing resin when cooperation.
In addition, following chemical formula: Mg has also been proposed 1-xm 2+ x(OH) 2represent complex metal hydroxide class (in formula, M 2+represent to be selected from Mn 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+, Zn 2+in divalent-metal ion at least a kind, X represents the scope of 0.001≤X≤0.005 or 0.7<X<0.9) magnesium hydroxide based flame retardant (referring to patent documentation 2).By using above-mentioned complex class magnesium hydroxide based flame retardant, can improve the acid resistance of formed body (telecommunication cable etc.).
Patent documentation 1: JP 2004-002884 communique
Patent documentation 2: Unexamined Patent 5-209084 communique
Summary of the invention
But the fire retardant of recording in patent documentation 1 and patent documentation 2 can not say sufficient aspect flame retardant resistance, reduction carbon monoxide generation and reduction smoke-producing amount.
Therefore, the object of the present invention is to provide a kind of fire retardant of magnesium hydroxide class and flame retardant resin composition and the formed body thereof that contains this fire retardant, wherein, when described fire retardant is matched with to resin, the flame retardant resistance of resin-formed body is high, and when resin-formed body burning, carbon monoxide generation and smoke-producing amount are few.
Fire retardant of the present invention is the fire retardant being made up of the magnesium hydroxide particles that contains transistion metal compound, it is characterized in that, above-mentioned transistion metal compound is at least a kind that is selected from copper compound, cobalt compound, nickel compound, zn cpds and titanium compound, it is 100～1000 quality ppm that any in above-mentioned transistion metal compound is converted into metal, it is below 1000 quality ppm that the total amount of above-mentioned copper compound, cobalt compound and nickel compound is converted into metal, and the total amount of above-mentioned zn cpds and titanium compound to be converted into metal be below 1000 quality ppm.
Fire retardant of the present invention is made up of the magnesium hydroxide particles that contains transistion metal compound, above-mentioned transistion metal compound is selected from least a kind in specific 5 kinds of compounds, any in above-claimed cpd is converted into metal and contains 100～1000 quality ppm, shown high flame retardant therefore be combined with the resin-formed body of this fire retardant, smoke-producing amount is also few.And, it is below 1000 quality ppm that the total amount of copper compound, cobalt compound and nickel compound is converted into metal, and it is below 1000 quality ppm that the total amount of above-mentioned zn cpds and titanium compound is converted into metal, therefore coordinated the growing amount of the resin-formed body of this fire retardant carbon monoxide of painted considerably less and when burning also few.
Herein, in magnesium hydroxide particles, the content of wantonly a kind in above-mentioned transistion metal compound is converted into metal and is necessary for 100～1000 quality ppm.This content is preferably 100～600 quality ppm, is more preferably 100～300 quality ppm.In addition, the content of transistion metal compound of more than two kinds is converted into metal and can be respectively 100～1000 quality ppm.
Be less than 100 quality ppm if the content of wantonly a kind of transistion metal compound is converted into metal, flame retardant resistance is insufficient, and it is many that the generation of carbon monoxide and smoke-producing amount also become.On the contrary, exceed 1000 quality ppm if the content of wantonly a kind of transistion metal compound is converted into metal, seriously painted by copper, cobalt, nickel, although do not exist by zinc, the painted problem of titanium, carbon monoxide reduces deleterious.Therefore, the total content of copper, cobalt, nickel is necessary for below 1000 quality ppm, and the total content of zinc, titanium is also necessary for below 1000 quality ppm simultaneously.
It should be noted that, it is generally acknowledged when improving the reason of flame retardant resistance is to burn that above-mentioned transition metal is as the catalyzer that promotes resin-formed body surface carbonization, the effect of performance blocking-up oxygen.In addition, transition metal is also used as oxide catalyst, makes the carbon monoxide generating easily be converted into carbonic acid gas.And transistion metal compound becomes activating oxide when burning, the unburnt coal smoke that absorption produces effectively.
As the form of transistion metal compound, can be the salt such as muriate, vitriol, nitrate, carboxylate salt, or oxide compound, oxyhydroxide, sulfide, can also be metal monomer.
As the method that makes magnesium hydroxide particles contain transistion metal compound, can be carrying out preparation of raw material stage before hydrothermal treatment consists or add after intended particle forms, also can in the time of the surface treatment of carrying out stearic acid described later etc., add simultaneously.In addition, can also adopt drying process to be blended in magnesium hydroxide powder.
BET (Brunauer, Emmett, the Teller) specific surface area of the above-mentioned magnesium hydroxide particles in fire retardant of the present invention is preferably 1～20m 2/ g, median size is preferably 0.5～5 μ m.
According to the present invention, because the BET specific surface area of the magnesium hydroxide particles as fire retardant is 1～20m 2/ g, median size is 0.5～5 μ m, requires characteristic therefore can meet the basis of flame retardant resin composition., BET specific surface area exceedes 20m 2in the situation of/g or median size less than 0.5 μ m, coordinate fire retardant in resin time, become easy generation aggegation again, cause the dispersiveness of fire retardant in resin to decline, cause the bad order of formed body, and extension elongation rate also declines.BET specific surface area is less than 1m 2when/g or median size exceed 5 μ m, although no problem in the dispersiveness of fire retardant in resin, flame retardant resistance declines, and tensile strength also declines.
Fire retardant of the present invention preferably carries out surface treatment with at least a kind of surface treatment agent being selected from higher fatty acid, higher fatty acid metal salt, anion surfactant, coupling agent, the ester class being formed by polyvalent alcohol, phosphoric acid ester to above-mentioned magnesium hydroxide particles.
According to the present invention, owing to the surface treatment agent of regulation, magnesium hydroxide particles having been carried out to surface treatment, therefore compared with not carrying out surface-treated particle, increase with the affinity of resin, therefore the dispersiveness of fire retardant in resin improves, tensile properties and shock-resistance improve, and the hydrophobic effect obtaining by coating surface treatment agent also increases water tolerance or acid resistance.
As surface treatment agent, preferably use particularly following compound.As higher fatty acid, for example can enumerate the carbonatomss such as stearic acid, sinapinic acid, palmitinic acid, lauric acid, behenic acid (behenic acid) is more than 10 higher fatty acid.In addition, the also an alkali metal salt of preferred above-mentioned higher fatty acid.As anion surfactant, can enumerate the sulfuric acid of the higher alcohols such as stearyl alcohol, oleyl alcohol or the sulfuric acid of polyglycol ether, amido linkage sulfuric acid, ester bond sulfuric acid, ester bond sulfonate, amido linkage sulfonate, ehter bond sulfonate, ehter bond alkylaryl sulphonate, ehter bond alkylaryl sulphonate, amido linkage alkylaryl sulphonate etc.As coupling agent, can enumerate vinyl Ethoxysilane, vinyl-tri-(2-methoxyl group-oxyethyl group) silane, γ-methacryloxypropyl trimethoxy silane, gamma-amino propyl trimethoxy silicane, β-(3, 4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrimethoxy silane, the silane coupling agents such as γ mercaptopropyitrimethoxy silane, or sec.-propyl three isostearoyl base titanic acid ester, sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester, sec.-propyl three (N-amino-ethyl-amino-ethyl) titanic acid ester, the aluminium class coupling agents such as titante coupling agent and ethanoyl aluminum alkoxide diiso propoxide such as sec.-propyl three decyl benzenesulfonyl titanic acid ester.As the ester class being formed by polyvalent alcohol, can enumerate the ester class that the polyvalent alcohol such as Zerol, glyceryl monooleate and lipid acid form.Phosphoric acid ester is monoesters or diester or both mixture that former phosphoric acid and oleyl alcohol, stearyl alcohol etc. form, and can enumerate the phosphoric acid esters such as above-mentioned acid type or an alkali metal salt or amine salt.
While using above-mentioned surface treatment agent to carry out surface treatment to magnesium hydroxide particles, can adopt known damp process or drying process.For example, as damp process, can in the slurry of magnesium hydroxide, add the surface treatment agent of liquid state or emulsion shape, mechanically mixing at the temperature till approximately 100 DEG C.As drying process, can under agitation liquid state, emulsion shape or solid-state surface treatment agent directly be joined in magnesium hydroxide powder by mixing machines such as Henschel mixers, under heating, mix as required.The addition of surface treatment agent can suitably be selected, and is preferably based on the weight of this magnesium hydroxide particles, is made as below approximately 10 quality %.
As required effects on surface magnesium hydroxide particles after treatment suitably wash, the operation such as dehydration, granulation, dry, pulverizing and classification, obtain the finished product form.
Flame retardant resin composition of the present invention is characterised in that, has coordinated the above-mentioned fire retardant of 5～500 mass parts with respect to 100 mass parts polyolefin resins.
As polyolefin resin, can enumerate the C such as polyethylene, polypropylene, ethylene/propene copolymer, polybutene, poly(4-methyl-1-pentene) herein, 2～C 8polymkeric substance or the multipolymer of alkene (alpha-olefin).
Flame retardant resin composition of the present invention is owing to coordinating the above-mentioned fire retardant of specified amount in polyolefin resin, therefore the high flame retardant of demonstrating, in the time of burning, carbon monoxide generation and smoke-producing amount are also few.
When the use level of fire retardant is less than 5 mass parts, be difficult to bring into play sufficient flame retardant effect, when use level exceedes 500 mass parts, the mechanical properties of resin (intensity, shock-resistance) variation.The use level of fire retardant is preferably 20～400 mass parts, more preferably coordinates 40～300 mass parts.
Formed body of the present invention is characterised in that by above-mentioned flame retardant resin composition and forms.
Because formed body of the present invention coordinates the above-mentioned fire retardant of specified amount as flame retardant resin composition in polyolefin resin, therefore the flame retardant resistance of formed body is high, and make formed body when burning, carbon monoxide generation and smoke-producing amount are also few.
Embodiment
Specifically describe the present invention according to the following examples, but the present invention is not limited thereto.
[embodiment 1]
(preparation of fire retardant)
Weigh 480g high purity MgCl 26H 2the polyethylene container made that 0 (MANAC system) capacity of putting into is 3L, adds 1L pure water to stir, preparation MgCl 2the aqueous solution.Under agitation slowly add wherein the NaOH aqueous solution (Mg of 510mL8.3N 2+mole number: OH-mole number is 1: 1.8), further add pure water, preparation 2L suspension liquid.This suspension liquid is transferred in the autoclave with liquid acceptance division of HASTELLOYC-276 system that capacity is 3L, under stirring, carries out the hydrothermal treatment consists of 5 hours in 140 DEG C.Slurry after vacuum filtration hydrothermal treatment consists, using with respect to solid state component is that 20 times of pure water more than capacity fully clean.Then, again put into pure water, preparation is with Mg (OH) 2solid component concentration is counted the emulsification slurry of 10g/dL.This emulsification slurry of 1L is put into SUS316 container made that capacity is 2L (with Mg (OH) 2solid state component quality meter is equivalent to 100g), heat while stirring this slurry until 80 DEG C.On the other hand, take 0.027g CuCl 22H 20, added and be equipped with in the glass beaker that the capacity of 100mL pure water is 200mL, by magnetic stirrer, the aqueous solution that this dissolving is obtained under agitation all joins (the accurate content of transistion metal compound utilizes the analysis of ICP (inductively coupled plasma, Inductively Coupled Plasma) method to obtain by aftermentioned) in the above-mentioned slurry that is heated to 80 DEG C.Then,, at 80 DEG C, add the aqueous solution of sodium stearate that is mixed with 5 quality % until with respect to Mg (OH) 2solid state component quality is counted 2.8 quality % with stearic acid, stirs and within 1 hour, carry out surface treatment at 80 DEG C, and vacuum filtration is washed (with respect to Mg (OH) 2solid state component quality is 5 times more than capacity), dry, pulverize, obtain fire retardant powder.
(manufacture of flame retardant resin composition and formed body)
Use acrylic resin (BC-6D processed of Japan Polypropylene Corp.) as polyolefin resin.With Labo Plasto Mill (Japan essence mechanism) at 180 DEG C by with respect to 100 mass parts acrylic resins being the above-mentioned fire retardant powder of 122 mass parts after mixing 5 minutes, at 180 DEG C, manufactures the formed body of indulging 100mm × horizontal 100mm × thick 3mm with pressure forming machine.
(assay method)
The fire retardant being obtained by aforesaid method and formed body are carried out to following analysis and evaluation.
(1) the transition metal quantitative analysis in fire retardant
At 600 DEG C, the fire retardant being obtained by above-mentioned compound method (magnesium hydroxide) powder is burnt till, dissolve completely with superfluous hydrochloric acid, adopt ICP method to measure levels of transition metals (Cu, Co, Ni, Zn, Ti).
(2) mensuration of BET specific surface area and median size
By the BET specific surface area of the fire retardant powder of determination of nitrogen adsorption gained, be all about 5m by the BET specific surface area that the result that size-grade distribution instrumentation is determined median size is all fire retardant powder 2/ g, median size is all about 1.2 μ m (also, including embodiment comparative example described later, being identical value).
(3) tone of formed body
The formed body of visual inspection gained, confirm that the formed body that can mix colours is evaluated as A, and painted formed body serious, that confirmation is difficult to toning is judged to be B.
(4) mensuration of electrothermal calefactive rate
According to ISO (the International Organization for Stand, International Organization for Standardization) 5660 part 1s, be that 660 DEG C, radiation quantity are 50kW/m in Heating temperature 2, extraction flow is 0.024m 3/ second condition under make each test sample burning with taper calorimeter (CONE CALORIMETER, the machine-processed C3 type of Japan's essence), according to the oxygen-consumption recording with the oxymeter maximum electrothermal calefactive rate that converts.It should be noted that, start from catching fire to measure until test sample burnouts till naturally extinguishing.The yardstick that this maximum electrothermal calefactive rate is flame retardant resistance.Maximum electrothermal calefactive rate is preferably 200kW/m 2below.
(5) mensuration of carbon monoxide (CO) generation
According to ISO5660 part 1, be that 660 DEG C, radiation quantity are 50kW/m in Heating temperature 2, extraction flow is 0.024m 3under the condition of/second, make each sample (formed body) burning with taper calorimeter (the machine-processed C3 type of Japan's essence), measure maximum CO with infrared spectrophotometer and produce concentration.It should be noted that, start from catching fire to measure until sample burnouts till naturally extinguishing.Maximum CO produces concentration and is preferably below 1.6 quality %.
(6) mensuration of smoke density
According to ISO5660 part 2, be that 660 DEG C, radiation quantity are 50kW/m in Heating temperature 2, extraction flow is 0.024m 3/ second condition under each test sample is burnt with taper calorimeter (Japan essence machine-processed C3 type), measure maximum smoke density (unit: m by laser penetrant method -1).
It should be noted that, start from catching fire to measure until test sample burnouts till naturally extinguishing.Maximum smoke density is preferably 0.057m -1below.
[embodiment 2,3 and comparative example 1～3]
Except CuCl 22H 2o is outside 0.134g (embodiment 2), 0.242g (embodiment 3), 0.013g (comparative example 2), 0.859g (comparative example 3), operates in the same manner with embodiment 1, obtains fire retardant powder.In comparative example 1, do not add and be dissolved with CuCl 22H 2the aqueous solution of O.Except aforesaid operations, manufacture in the same manner fire retardant and formed body with embodiment 1, carry out assay.The result of embodiment 1～3 and comparative example 1～3 is as shown in table 1.
[table 1]
? Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1 Comparative example 2 Comparative example 3
Cu (quality ppm) 112 490 925 1 56 3267
Co (quality ppm) <1 <1 <1 <1 <1 <1
Ni (quality ppm) 1 1 1 1 1 1
Zn (quality ppm) 2 2 2 2 2 2
Ti (quality ppm) <1 <1 <1 <1 <1 <1
Cu+Co+Ni (quality ppm) <114 <492 <927 <3 <58 <3269
Zn+Ti (quality ppm) <3 <3 <3 <3 <3 <3
Maximum electrothermal calefactive rate (kW/m 2) 179 184 198 221 218 199
Maximum CO produces concentration (quality %) 1.37 1.52 1.54 1.8 1.71 1.54
Maximum smoke density (m -1) 0.055 0.056 0.057 0.061 0.06 0.057
Tone A A A A A B
[embodiment 4～6, comparative example 4,5]
While preparing fire retardant, except weighing and adding 0.061g (embodiment 4), 0.162g (embodiment 5), 0.364g (embodiment 6), 0.004g (comparative example 4) and 0.606g (comparative example 5) CoCl 26H 2outside O, manufacture in the same manner fire retardant and formed body with embodiment 1, carry out assay.Result is as shown in table 2.
[table 2]
? Embodiment 4 Embodiment 5 Embodiment 6 Comparative example 4 Comparative example 5
Cu (quality ppm) 1 1 1 1 1
Co (quality ppm) 156 388 875 13 1589
Ni (quality ppm) 1 1 1 1 1
Zn (quality ppm) 2 2 2 2 2
Ti (quality ppm) <1 <1 <1 <1 <1
Cu+Co+Ni (quality ppm) 158 390 877 15 1591
Zn+Ti (quality ppm) <3 <3 <3 <3 <3
Maximum electrothermal calefactive rate (kW/m 2) 193 194 195 221 202
Maximum CO produces concentration (quality %) 1.35 1.38 1.47 1.77 1.65
Maximum smoke density (m -1) 0.054 0.056 0.057 0.06 0.061
Tone A A A A B
[embodiment 7～9, comparative example 6,7]
While preparing fire retardant, except weighing and adding 0.101g (embodiment 7), 0.263g (embodiment 8), 0.324g (embodiment 9), 0.032g (comparative example 6) and 1.174g (comparative example 7) NiCl 26H 2outside O, manufacture in the same manner fire retardant and formed body with embodiment 1, carry out assay.Result is as shown in table 3.
[table 3]
? Embodiment 7 Embodiment 8 Embodiment 9 Comparative example 6 Comparative example 7
Cu (quality ppm) 1 1 1 1 1
Co (quality ppm) <1 <1 <1 <1 <1
Ni (quality ppm) 258 642 774 84 2893
Zn (quality ppm) 2 2 2 2 2
Ti (quality ppm) <1 <1 <1 <1 <1
Cu+Co+Ni (quality ppm) <260 <644 <776 <86 <2895
Zn+Ti (quality ppm) <3 <3 <3 <3 <3
Maximum electrothermal calefactive rate (kW/m 2) 183 190 197 220 198
Maximum CO produces concentration (quality %) 1.32 1.4 1.45 1.74 1.46
Maximum smoke density (m -1) 0.055 0.056 0.057 0.061 0.057
Tone A A A A B
[embodiment 10～12, comparative example 8,9]
While preparing fire retardant, except weighing and adding 0.077g (embodiment 10), 0.159g (embodiment 11), 0.341g (embodiment 12), 0.027g (comparative example 8) and 2.274g (comparative example 9) Zn (NO 3) 26H 2outside O, manufacture in the same manner fire retardant and formed body with embodiment 1, carry out assay.Result is as shown in table 4.
[table 4]
? Embodiment 10 Embodiment 11 Embodiment 12 Comparative example 8 Comparative example 9
Cu (quality ppm) 1 1 1 1 1
Co (quality ppm) <1 <1 <1 <1 <1
Ni (quality ppm) 1 1 1 1 1
Zn (quality ppm) 175 353 763 66 5044
Ti (quality ppm) <1 <1 <1 <1 <1
Cu+Co+Ni (quality ppm) <3 <3 <3 <3 <3
Zn+Ti (quality ppm) <176 <354 <764 <67 <5045
Maximum electrothermal calefactive rate (kW/m 2) 173 191 195 219 205
The sternly raw concentration (quality %) of maximum CO 1.33 1.45 1.53 1.69 1.68
Maximum smoke density (m -1) 0.054 0.055 0.056 0.061 0.059
Tone A A A A A
[embodiment 13～15, comparative example 10,11]
While preparing fire retardant, except weighing and adding 0.119g (embodiment 13), 0.267g (embodiment 14), 0.475g (embodiment 15), 0.018g (comparative example 10) and 2.373g (comparative example 11) [(CH 3) 2cHO] 4outside Ti, manufacture in the same manner fire retardant and formed body with embodiment 1, carry out assay.Result is as shown in table 5.
[table 5]
? Embodiment 13 Embodiment 14 Embodiment 15 Comparative example 10 Comparative example 11
Cu (quality ppm) 1 1 1 1 1
Co (quality ppm) <1 <1 <1 <1 <1
Ni (quality ppm) 1 1 1 1 1
Zn (quality ppm) 2 2 2 2 2
Ti (quality ppm) 230 466 826 28 4009
Cu+Co+Ni (quality ppm) <3 <3 <3 <3 <3
Zn+Ti (quality ppm) 232 468 828 30 4011
Maximum electrothermal calefactive rate (kW/m 2) 190 193 199 220 205
Maximum CO produces concentration (quality %) 1.26 1.38 1.52 1.63 1.71
Maximum smoke density (m -1) 0.055 0.056 0.057 0.06 0.06
Tone A A A A A
[embodiment 16]
While preparing fire retardant, except weighing 0.027g CuCl 22H 2o and 0.068g Zn (NO 3) 26H 2o, add outside this whole 100mL mixed aqueous solutions, manufacture in the same manner fire retardant and formed body with embodiment 1, carry out assay.
[embodiment 17]
While preparing fire retardant, except weighing 0.148g CuCl 22H 2o and 0.205g Zn (NO 3) 26H 2o, add outside this whole 100mL mixed aqueous solutions, manufacture in the same manner fire retardant and formed body with embodiment 1, carry out assay.
[embodiment 18]
While preparing fire retardant, except weighing 0.188g CuCl 22H 2o and 0.409g Zn (NO 3) 26H 2o, add outside this whole 100mL mixed aqueous solutions, manufacture in the same manner fire retardant and formed body with embodiment 1, carry out assay.
[comparative example 12]
While preparing fire retardant, except weighing 0.011g CuCl 22H 2o and 0.032g Zn (NO 3) 26H 2o, add outside this whole 100mL mixed aqueous solutions, manufacture in the same manner fire retardant and formed body with embodiment 1, carry out assay.
[comparative example 13]
While preparing fire retardant, except weighing O.403g CuCl 22H 2o and O.955g Zn (NO 3) 26H 2o, add outside this whole 1OOmL mixed aqueous solutions, manufacture in the same manner fire retardant and formed body with embodiment 1, carry out assay.
The result of embodiment 16～18 and comparative example 12,13 is as shown in table 6.
[table 6]
? Embodiment 16 Embodiment 17 Embodiment 18 Comparative example 12 Comparative example 13
Cu (quality ppm) 108 542 716 45 1450
Co (quality ppm) <1 <1 <1 <1 <1
Ni (quality ppm) 1 1 1 1 1
Zn (quality ppm) 147 433 879 68 2167
Ti (quality ppm) <1 <1 <1 <1 <1
Cu+Co+Ni (quality ppm) <110 <544 <718 <47 <1452
Zn+Ti (quality ppm) <148 <434 <880 <69 <2168
Maximum electrothermal calefactive rate (kW/m 2) 178 186 195 217 199
Maximum CO produces concentration (quality %) 1.41 1.44 1.45 1.72 1.49
Maximum smoke density (m -1) 0.054 0.055 0.056 0.06 0.058
Tone A A A A B
[embodiment 19]
While preparing fire retardant, except weighing 0.054g CuCl 22H 2o, 0.044g CoCl 26H 2o, NiCl O.053g 26H 2o, 0.091g Zn (NO 3) 26H 2o and O.089g[(CH 3) 2cHO] 4ti, add outside this whole 1OOmL mixed aqueous solutions, manufacture in the same manner fire retardant and formed body with embodiment 1, carry out assay.
[comparative example 14]
While preparing fire retardant, except weighing O.008g CuCl 22H 2o, 0.032g CoCl 26H 2o, NiCl O.008g 26H 2o, Zn (NO O.032g 3) 26H 2o and 0.030g[(CH 3) 2cHO] 4ti, add outside this whole 100mL mixed aqueous solutions, manufacture in the same manner fire retardant and formed body with embodiment 1, carry out assay.
[comparative example 15]
While preparing fire retardant, except weighing O.081g CuCl 22H 2o, 0.202g CoCl 26H 2o, 0.182g NiCl 26H 2o, Zn (NO O.227g 3) 26H 2o and 0.326g[(CH 3) 2cHO] 4ti, add outside this whole 100mL mixed aqueous solutions, manufacture in the same manner fire retardant and formed body with embodiment 1, carry out assay.
[comparative example 16]
While preparing fire retardant, except weighing 1.342g CuCl 22H 2o, 0.687g CoCl 26H 2o, 1.579g NiCl 26H 2o, 1.183g Zn (NO 3) 26H 2o and 2.729g[(CH 3) 2cHO] 4ti, add outside this whole 100mL mixed aqueous solutions, manufacture in the same manner fire retardant and formed body with embodiment 1, carry out assay.
The result of embodiment 19 and comparative example 14～16 is as shown in table 7.
[table 71
? Embodiment 19 Comparative example 14 Comparative example 15 Comparative example 16
Cu (quality ppm) 202 27 310 5005
Co (quality ppm) 113 82 505 1744
Ni (quality ppm) 131 15 440 3867
Zn (quality ppm) 196 71 499 2691
Ti (quality ppm) 150 54 558 4639
Cu+Co+Ni (quality ppm) 446 124 1255 10616
Zn+Ti (quality ppm) 346 125 1057 7330
Maximum electrothermal calefactive rate (kW/m 2) 180 217 184 197
Maximum CO produces concentration (quality %) 1.33 1.7 1.4 1.59
Maximum smoke density (m -1) 0.054 0.059 0.055 0.058
Tone A A B B
(result)
From table 1～7, in embodiment, the amount of the specific transistion metal compound containing in fire retardant (magnesium hydroxide) all within the limits prescribed, therefore made to coordinate formed body when burning of this fire retardant, shown high flame retardant, and the generation of carbon monoxide and cigarette is also few.
On the other hand, in comparative example 1,2,4,6,8,10,12 and 14, because the content (being scaled metal) of specific transistion metal compound is lower than 100 quality ppm, therefore flame retardant resistance is insufficient, the generation of carbon monoxide and cigarette is also many.As shown in comparative example 14, even if only the total amount of transistion metal compound (being converted into metal) is for more than 100ppm, above-mentioned effect is also insufficient.
In addition, in comparative example 3,5,7,13 and 16, because the total content of copper, cobalt and nickel exceedes 1000 quality ppm, therefore formed body by seriously painted, is difficult to toning.In addition, if the content of above-mentioned transition metal exceedes 1000 quality ppm, to the slightly negative impact of above-mentioned effect.In comparative example 9,11, the total content of zinc and titanium exceedes 1000 quality ppm, therefore even if tone is good, above-mentioned effect is also on duty mutually.
Utilizability in industry
The present invention is preferably used as the Halogen based flame retardant that molding synthetic resin body is used.Particularly can be widely used in outer within doors cable or the thin wire coating material for household appliances, automobile etc.

Claims (5)

1. fire retardant, described fire retardant is made up of the magnesium hydroxide particles that contains transistion metal compound, it is characterized in that,
Described transistion metal compound is made up of copper compound, cobalt compound, nickel compound, zn cpds and titanium compound,
In described transistion metal compound, to be converted into metal be 100～600 quality ppm to any content,
It is below 1000 quality ppm that the total amount of described copper compound, cobalt compound and nickel compound is converted into metal, and the total amount of described zn cpds and titanium compound to be converted into metal be below 1000 quality ppm.
2. fire retardant as claimed in claim 1, is characterized in that, the BET specific surface area of described magnesium hydroxide particles is 1～20m 2/ g, median size is 0.5～5 μ m.
3. fire retardant as claimed in claim 1 or 2, it is characterized in that, described magnesium hydroxide particles uses at least a kind of surface treatment agent being selected from higher fatty acid, higher fatty acid metal salt, anion surfactant, coupling agent, the ester class being formed by polyvalent alcohol, phosphoric acid ester to carry out surface treatment.
4. flame retardant resin composition, is characterized in that, described flame retardant resin composition, with respect to 100 mass parts polyolefin resines, has coordinated the fire retardant described in any one in 5～500 mass parts claims 1～3.
5. formed body, described formed body is made up of flame retardant resin composition claimed in claim 4.
CN201410116859.9A 2005-10-25 2006-10-24 Flame retardant, flame-retardant resin composition and molded body Pending CN103923344A (en)

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